Production and use of dyestuffs



'UNITED STATES Patented Sept. 8, 1936 T OFFICE 2,053,274 PRODUCTION- AND se or nrns'rurrs George Holland Ellis and Frank Brown, Spondon, near Derby, England, assignors to @elanese Corporation of America, a corporation of Delaware No Drawing. Application February 7, 1933, Serial No."655,615. In Great Britain February 17,

' 19 Claims.

In our co-pending U. S. application S. No.

' 655,614 we have described a series of valuable anthraquinone derivativescontaining in one a position a hydroxyl group, in a second a-position an amino or a non-aromatically substituted amino group and in a third iii-position an aryl-- amino group, which compounds constitute very valuable colouring matters for cellulose ester and ether materials.

These new dyestuffs may berepresented by the following formula:

A-Y z I wherein A represents anthraquinone and X, Y and Z represent alpha substituents, one of which is a hydroxyl group,. one an aryl substituted amino group and the third a free amino group, or a non-aromatically'substituted amino group, i. e. an amino group substituted only by a wholly aliphatic residue or other residue such that car-' bon of an aromatic nucleus if present therein is not directly attached to the amino nitrogen. By means of dyestuffs oi this series, more especially by dyestuffs in which the arylamino group is in a. para position'to-either the hydroxyl group or the other amino group, especially the latter, blue shades of exceptional resistance to the usual agencies may be obtained. For example l-amino- 4-phenylamino-5-hydroxy anthraquinone dyes cellulose acetate material in pure blue shades of excellent fastness to light and to light in the presence of acid fumes such as combustion prodter as those in the 1:4:5-positions or they may be of difierent character. For example further hydroxy, amino, aliphatically substituted amino,

or arylamino groups may be present but especially a further hydroxyl group. Particular mention may be made of compounds containing as further substituent an oz-hYdI'OXYl group, for instance 1 amino -'4 phenylamino-5:8-dioxy-anth'raquinone and its isomer 4-amino-8--phenyl-,

amino-1:S-dioxy-anthraquinone, which dye cellulose acetate in greenish blue shades of exceptional resistance to the actionof light in the pres-- v ence of acid.

The dyestufis may be represented by the general formula:-

wherein A represents ananthraquinone residue,

X, Y and Z a-substituents, one of which is a hydroxyl group, one an arylamino group and the third an unsubstituted amino group or a nonaromatically substituted amino group, and B represents a substituent of the type of X, Y and Z or of a different type.

We have also found that anthraquinone derivatives containing a hydroxy group, an amino or aliphatically substituted amino group and an arylamino group, and in which these groups have other than .the 1:4:5-orientation are also valuable colouring matters. Thisv is more particularly thecase if at leasttwo of the three characteristic substituents, preferably the two amino substituents are in para position to each other as, for instance, in 1-amino-2-oxy-4-phenylamino-anthraquinone.

As in the case of the anthraquinone derivatives of U. 8. application S. No. 655,614 the aryl .substituent of the aryl substituted amino group may be of anydesired character, for example of the benzene, naphthalene or. other series, but is pref-- erably of the benzene series. It may be substituted in any desired manner. Thus, for example,

it maycontain alkyl, hydroxy, alkoxy, amino,.

halogen or other substituents. Special reference may be adeto the presence of acidylamino groups, to; increase the afiinity of the dyestuff for the material, as described in co-pending U. S. application S. No. 655,617 filed February 7, 1933.

Again, increased afiinity may be imparted by the presence of an alkyl group or other substituent in the meta-position to the amino group, as described in co-pending U. S. application S. No.

2 655,613 filed February 7, 1933, Patent Number 2,029,312 of February 4, 1936, and alkyloxy groups especially in the ortho-position to the amino group may be present, whereby a still further increase of resistance to acid fading may be secured (see co-pending U. S. application S. No. 655,616 filed February 7, 1933, Patent Number 2,029,313 of February 4, 1936). The second hydrogen atom 01' the aryl substituted amino group may alsorbe substituted, for example by means of an alkyl or other aliphatic residue. The substituent of the non-aromatically substituted amino group of the anthraquinone derivatives may be of any desired character provided that the amino nitrogen is not directly attached to carbon of an aromatic nucleus of the substituent. As examples of suitable non-aromatic substituents mention may be made of methyl or ethyl or other alkyl groups, substituted alkyl groups, for example hydroxy-ethyl, hydroxy-propyl or 'y-chlor-fi-hydroxy propyl, aliphatic acidyl groups, for example acetyl, hydrogenized aromatic residues for example cyclohexyl or substituted cyclohexyl groups, and aralkyl groups or hydrogenized aralkyl groups for example benzyl or hydrogen- --ized benzyl residues. If desired the substituent duced from anthraquinone compounds substituted in the 1:4:5-positions and/or other appropriate positions by reactive atoms or groups byreplacing the said reactive atoms or groups by or converting them into the desired hydroxyl, amino;

arylamino and/or other desired groups or atoms. It will be appreciated that the parent compounds may already contain one or other of the desired groups or atoms in the appropriate position in the nucleus and in such case it may only be necessary to replace one or two replaceable atoms or groups by hydroxyl, amino, arylamino, or other groups. Other parent materials may comprise compounds containing the desired hydroxyl, amino, substituted amino, and other atoms or groups in the required positions and in addition other groups, for example sulphonic groups, which may be readily eliminated in order to obtain the desired compounds.

It will be appreciated that the dyestuffs of the' genera1formula:-

previously given may be obtained from tetrasub'stituted anthraqulnones of which threesubstituents are three of X Y Z and B while the fourth is a replaceable or convertible atom or groupyby treatment soas to convert into the fourth'of the required substituents the said replaceable or convertible atom or group.

I As examples of replaceable or convertible atoms or groups mention may be madeof sulphonic groups, hydroxyl, alkoxy, and aryloxy groups, nitro groups, amino and substituted amino groups. and chlorine or other halogen atoms.

with ammonia or substituted ammonias.

Sulphonic groups may for instance be converted into hydroxyl groups by the action of alkalies, particularly Weak alkalies such as milk of lime or solutions of alkali carbonates, or into amino or substituted amino groups by the action of am:- monia or the corresponding substituted ammonias. Hydroxyl or. alkoxyl groups may similarly be converted into amino groups or substituted amino groups by the action of ammonia or aliphatic or aromatic amines. Nitro groups may for instance be converted into amino groups by reduction, or into substituted amino groups by direct reaction with aliphatic or aromatic amines. Thehydrogen of amino groups may be substituted by acyl or hydrocarbon or other radicles by the action of appropriate acylating, alkylating or aralkylating or other agents. Chlorine and other halogen atoms may readily be converted into hydroxyl groups by the action forinstance of I concentrated sulphuric acid, especially in the presence of boric acid, or by the action of alkalies, especially weak alkalies such as calcium hydroxide. Again, they may be converted into amino groups or substituted amino groups by reaction One convenient method of replacing halogen atoms by amino groups is to condense the halogen compound with an arylsulphonamide phthalimide or other acid amide and then to saponify the acidylamino compound so obtained.

The. replacement of hydroxyl groups by amino or hydroxyl and amino groups by substituted amino groups by the direct action of ammonia or substituted ammonia may frequently be facilitat-,.

ed by first reducing the anthraquinone compound to a'leu'co derivative. Such is especially the case when compounds contain hydroxyl or hydroxyl and amino groups in the 1:4-positions. The amidationv of reduced hydroxy anthraquinone compounds may if desired be efiected in the presence of inorganic alkali in the manner described in U. S. application S. No. 331,390 filed 9th January, 1929'Patent Number 1,969,748 of August 14,

The replacement or hydroxyl groups by arylamino groups by the action of aromatic amines may be efiected in the presence of boric acid or similarly acting substances. I

As examples of suitable parent materials containing reactive groups mention may be made of the following:-4:5-diaminoor 4:5-dinitrochrysaz'in, 4:8-diaminoor 4:8-dinitro-anthrarufin, 4:5-dichlorchrysazin, dichloroanthrarufin (obtainable for instance by action of sulphuryl chloride on anthrarufin) 1:514:8- or 'l:8:4:5-dichlor-dinitro anthraquinone, 1:4:528-tetraoxyanthraquinone, 122:5:8 tetraoxyanthraquinone,

proportion of ammonia so as'to replace only one 01' "the para-hydroxyl groups, and the resulting product subjected to the action of aniline, paratoluidine or other aromatic amine in 'order to efiect replacement of the other of the parahydroxy groups. Again, 1-amino-4z5z8-trihydrox-y anthraquinone maybe subjected to the 15 ing matters may be converted into concentrated action of aniline so as to replace .the 4-hydroxyl group by an anilido residue with the formation of,

1 amino 4 anilido-5z8-dihydroxy anthraquinone. r

For the production of the valuable aminodioxy-arylamino-anthraquinones especially those in which the substituents are in a-position it has been found particularly advantageous to take a dioxy-anthraquinone containing two suitable substituents, e. g. halogen or nitro, and to replace the latter in succession in either order by an arylamino group and an amino group which is unsub-' stitutedor. is non-aromatically substituted. If, of course, one of the two substituents is already of the desired character only the remaining one may require replacement.

Particular mention may be made of the production of the especially valuable aminodioxyarylan arylamino group, the remaining nitro group being then reduced to amino or replaced by an aliphatically substituted amino'group by the *action of an aliphatic amine, e. g. methylamine or oxyethylamine;

In this manner 4-amino-8-phenylamino-l:5- dioxyanthraquinone may be obtained-from di-,

nitro-anthrarufin and d-amino-fi-phenyl-amino- 1 8-dioxy-anthraquinone from dinitro-chrysazin..

The replacement of the nitro group by arylamino is conveniently efiected by heating the dinitro-dioxy-anthraquinone with an arylamine at water bath temperatures for several hours, e. g. 8 hours. group may be effected in anydesired way but we have found that particularly good results are obtained when reduction is eifected by means of' reducing sugars and alkalies in aqueous media,

for example aqueous glucose and caustic soda.

The new-colouring matters, as indicated above,

are of especial value for the colouration of cellulose acetate and other cellulose ester or ether As examples of such, other esters and materials. ethers reference may be made to cellulose formate, propionate or butyrate or the products obtainable by treating alkalized cellulose with esterifying agents or the ethyl, benzyl or bther ethers of cellulose. They may also be applied to mixed materials comprising .one or more of the aforesaid cellulose esters or ethers in admixture with other textile fibres, for example wool, silk or other animal fibres, or cotton, regenerated cellulose or other 'cellulosic materials. Such other fibres may be coloured by the same dyestuffs as the cellulose esters or ethers when they possess the requisite afiinity, or they may be coloured either in the same or diiferent shades by means of other dyestufis, either before, after or simultaneously with the colouration of the cellulose esters or ethers.

The said colouring matters maybe appliedto textile materials either in the reduced state. that is by a. vat process or in the form of free leuco compounds in the manner described in U. S. ap-

plication S. No. 459,828 filed 5th June 1930, Patent- The reduction of the remaining nitro.

for example, by grinding (e. g. in colloid mills),

by dissolving in a solvent and mixing with water containing or not containing protective colloids and/0r dispersators, or by treatment with dispersing agents whether aloneor in the presence I of protective colloids and/or liquids, e. g. water. Preparations intended for vattingmay contain reducing agents, alkali or the like, e. g. alkali salts of hydroxyandpolyhydroxy cyclic compounds (see U. S. Patent No.- 1,716,720) As examples of dispersing agents or protective colloids mention may be made of the following:.

Sulphoaromatic fatty acid compounds, e. g. sulpho-benzene palmitic 7 acid compound (see U. S. Patent No. 1,694,413).

Sulphoaromatic ricinoleic, acid componds, e. g. sulphonaphthalenericinoleic acid (see U. S. Pat ent No. 1,840,572) I Naphthenic acids or other carbocyclic compoundscontaining salt-forming groups or salts of such acids or compounds (see U. S. Patent No. 1,618,414).

Sulphonated oil compounds, e. g. sulphonated castor oil.

Sulphuricesters of higher aliphatic alcohols.

Furfural-naphthalene sulphonic acid compounds (see U. S. application S. No. 390,423 filed 4th September, 1929), Patent Number 1,928,647 of October 3, 1933. Y

- Resino-naphthalene sulphonic acid compounds (see U. S. application S. No. 390,424 filed 4th September, 1929), Patent Number 1,959,352 of May 1 sulphonic acids. q

Sulphite cellulose waste liquor or its constitue.

Formaldehyde naphthalene sulphonic acid compounds.

Alkyl-, cycltfilkyh. and aralkyl-naphthalene Sulphonic acid compounds of distillation residues of benzaldehyde.

. Carbohydrates including gums.

Glue and gelatine.

By addition of or dilution with water the aforesaid preparations containing unreduced unsulphonated'colouring matters yield aqueous suspensions or colloidal solutions which may be directlyemployed for the colouration of cellulose acetate or other organic substitution derivatives of cellulose. The preparations containing reduced or unreduced colouring matters may be employed for the preparation of dye vats for the colouration of cellulose acetate or other organic substitution derivatives of cellulose or other textile material's.

, The colouring matters may be applied to the materials in any desired manner, for example by dyeing or other method of uniform application,

or by printing, stencilling or other method of local application. If desired the new colouring .matters may be employed for the colouration of stannous chloride discharges in the manner described in U. S. application S. No. 523,837, filed 19th March, 1931.

The invention is illustrated but not limited by the following examples:-

Example 1 Preparation of 4-amino-8-phenylamino-1:5- dioxy anthraquinone.

l part of pure 4:8-dinitro-anthrarufin is heated on the water bath with 4 parts of aniline for 8 hours, during which time the colour of the solution changes from yellow to greenish- -blue. Upon pouring the cooled melt into an excess of dilute hydrochloric acid there is obtain a. suspension of 4-nitro-8-phenylamino- 1 5-dioxy-anthraquinone.

This is filtered oil and reduced to 4-amino-8-.

phenylamino-l:5-dioxy-anthraquinone by heating at C. for 1 hour with 30 parts of water, 0.5 part caustic soda,'and 1.5 parts of glucose. The new dyestufi is obtained as a reddish blue powder, soluble in methylated spirit to a greenishblue solution.

Example 2 Preparation of 4-amino-5-paratolylamino-1:8- dioxy-anthraquinone.

1 part of 4:5-dinitro-1:8-dioxy-anthraquinone is heated on the water bath for 8 hours with 4 parts of paratoluidine. The reaction follows an analogous course to that of Example 1, subsequent isolation and reduction proceeding as detailed therein.

Example 3 Arylidation of 1 4 5-trioxy-8-amino-anthraquinone.

1 part of 1:4:5-trioxy-8-amino-anthraquinone, 1 part of boric acid, and 5 parts of orthoanisidine, are heated at the boiling point fora few minutes, the solution becoming bright blue. After separating from excess of o-anisidine, the new dyestuff may be purified ,by recrystallization from amyl alcohol.

Example 4 1 part of l-amino-4:528-trioxyanthraquinone and 1 part of boric acid are boiled with 10 parts of aniline for half an hour. I

After separation from excess aniline a product is obtained which is readily dispersible in water by means of Turkey red oil or other dispersing agent and from the dispersions so obtained yields on cellulose acetate materials blue shades exceptionally resistant to the combined actions of light and acid.

Example 5 To dye 10 kilograms of cellulose acetate knit fabric a pure blue shade.

1 kilogram of a paste consisting of one part of finely divided 4-amino-8-phenylamino-1:5-dioxyanthraquinone, 6 parts of water, and 3 parts .of Turkey red oil (50%) is heated to the boil with 10 litres of 2.5 grams per litre soap solution, with stirring, and strained through a filter cloth into a dyebath containing 300 litres of 2.5 grams per litre soap solution. The previously scouredv cellulose acetate fabric is now entered in rope form,'and dyeing commenced cold or luke warm. the temperature being raised slowly to 80 C. and maintained thereat for 1 hours or till the requisite shade is achieved. The goods are now washed off thoroughly and. dried or otherwise treated as desired or requisite.

For printing cellulose acetate goods the dyestufi paste is suitably diluted and thickened with a gum thickening paste which may also contain swelling agents for cellulose acetate, e. g. meth- OIII (I) Y wherein Y represents an aryl amino group and Z' an amino group or a non-aromatically substituted amino group.

3. As a new product, l-amino-5-phenylamino- 4 8-dioxyanthraquinone.

4. As new products, amino anthraquinone derivatives of the general formula:-

I ll 2 0 wherein Y represents an arylamino group and Z an amino group or a non-aromatically substituted amino group.

5. As new products, amino anthraquinone de- 'rivatives containing a single arylamino group,

said anthraquinone derivatives being a-a-dihydroxy anthraquinones substituted in one of the remaining a-positions by an arylamino group of the benzene series and in the other by a substituent selected from the group consisting of amino and non-aromatically substituted amino groups.

6. As new products, amino anthraquinone derivatives of thegeneral formula:---

0 OHOY IAI- \ I Z O H wherein Y represents an arylamino group of the benzene series and Z an amino group.

7. As new products, amino anthraquinone derivatives of the general formula:--

wherein Y represents an arylamino group of the benzene series and Z an amino group.

8. Process for the production of new amino anthraquinone derivatives containing a single arylamino group, said anthraquinone derivatives being a-a-dihydroxy anthraquinones substituted hydroxy-anthraquinone to the action of an aryl- 20 .stufls from din'itro-anthrarufln or dinitro-' chrysin one of the remaining u-POSltlOllS by an arylamino group and in the other by a substituent selected from the group of amino and non-aromatlcally substituted amino groups, which coinprises subjecting an a-a-dihydroxy anthraquinone containing replaceable atoms or groups in the remaining tat-positions to treatment to replace one ot-the said replaceable groups by an arylam'ino group and to replace the otherof the said groups by a substituent selected from the group consisting of amino and non-aromatically substituted amino groups.

9."Process for the production of 1-amino-4- arylamino-5:8-dihydroxy-anthraquinone wherein the arylamlno group is oi the benzene series, which comprises subjecting 1-amino-4t5z8-triamine oi the benzene series.

10. Process for the production of new dyeazin, which comprises replacing one nitro group by an arylamino group by the action of an arylamine and thereafter reducing the product.

11. Process for the production of new dyestufls from dinltro-anthrarufln .or dinitrochrysazin, which comprises replacing one nitro group by an aliphatically substituted amino group by the action of an aliphatic amine and-thereafter replacing the other nitro group by an aryl-- amino group by the action of an arylamine.

12. Process for the production ot'new dyestuffs from dinitro-anthrarufln or dinitro chrysazin,

which comprises replacing one nitro group by an arylamino group or the benzene series by the action of an arylamine of the benzene series and thereafter reducing the product.

13. Process for the production 01' a new dyestufl! from dinit'ro-anthraruiin, which comprises replacing one nitro group by a phenylamino group by the action of aniline and thereafter reducing.

the resulting product.

14. Process for the production or new dyestuffs consisting of amino and non-aromatically sub-- stituted amino groups.

16. A composition of matter comprising a dispersing agent and 1-amino-5-ary1amine-4z'8- dihydrox'y-anthraquinone.

1'7. Process for the coloration of organic derivatives of cellulose, which comprises applying thereto an amino anthraquinone derivative containing a single arylamino'g'roup, said anthraquinone derivative being an .a-a-dihydroxy anthraquinone substituted in one of the remaining a-POSitiOllS by an arylamino group and in the other by a substituent selected, irom the groupconsisting of amino and non-aromatically substituted amino groups. 18. Process for the coloura'tion of cellulose acetate, which comprises applying thereto an'amino anthraquinone derivative containing a single arylamino group, said anthraquinone, derivative being an a-a dihydroxy anthraquinone substituted in one of the remaining a-DOSltiOIlS by an arylamino group and in the other by a substituent selected from the group consisting. of amino andv non-aromatically substituted amino groups.

19. Processfor the colouration of cellulose acetate, which comprises applying thereto 1:5 -dihydroxy-4-phenylamino-8-ainino anthraquinone.

- GEORGE HOLLAND mus. FRANK BROWN. 

